Agent and method for dyeing keratin fibers

ABSTRACT

The present invention relates to a fiber-dyeing agent (A) prepared by mixing two components (A1) and (A2), said agent being characterized in that component (A1) contains at least one compound of formula (I)                    
     wherein X denotes a halogen atom, a methoxy group or an ethoxy group; Y denotes an oxygen atom, a sulfur atom or a selenium atom; R1 and R2 are equal or different and independently of each other denote hydrogen, a halogen atom, a (C 1 -C 4 )-alkyl group, a halogen-substituted (C 1 -C 4 )-alkyl group, a (C 1 -C 4 )-alkoxy group, a nitro group, an acetamido group or an NR a R b  group, wherein the R a  and R b  groups are equal or different and independently of each other denote hydrogen, a (C 1 -C 4 )-alkyl group, an optionally substituted aromatic carbon ring or a (C 1 -C 4 )-alkanecarbonyl group, or R a  and R b  together with the nitrogen atom form a heterocyclic (C 3 -C 6 ) group, and component (A2) contains at least one compound from the group consisting of amines, aminonitrobenzenes and phenols; to a method for dyeing hair by use of said agent, and to a multicomponent kit.

The object of the present invention is an agent for dyeing keratinfibers, for example silk, wool or hair, particularly human hair, andwhich contains a combination of (i) at least one4-nitro-2,1,3-benzoxadiazole derivative, 4-nitro-2,1,3-benzothiadiazolederivative or 4-nitro-2,1,3-benzoselenadiazole derivative and (ii) atleast one amine, aminonitrobenzene or phenol, and a method for dyeingkeratin fibers by use of said dyeing agent.

Depending on the starting color of the hair to be dyed and the desiredfinal result, hair colorants are divided mainly into oxidative colorantsand toners. Oxidative hair colorants are very well suited for coveringhigher proportions of gray hair. The oxidative colorants used for a grayproportion of up to 50% are usually referred to as oxidative tonerswhereas the oxidative colorants used for hair with a proportion of grayhair greater than 50%, or for “brightening”, are usually referred to asoxidative colorants. Direct dyes are contained mainly in non-oxidativecolorants (toners). Because of their small molecular size, some directdyes, for example the nitro dyes, can penetrate into hair and—at leastin the outer regions—dye it directly. Such toners are very gentle to thehair and as a rule can withstand six to eight hair washings. Directdyes, particularly nitro dyes, are also frequently used in oxidativecolorants to create certain shades or to intensify the color.

Nevertheless, there still exists a great need for colorants capable ofboth intense and gentle coloration under mild conditions.

Surprisingly, we have now found that by use of a combination of (i) atleast one-4-nitro-2,1,3-benzoxadiazole derivative,4-nitro-2,1,3-benzothiadiazole derivative or4-nitro-2,1,3-benzoselenadiazole derivative and (ii) at least one amine,aminonitrobenzene or phenol, intense colorations with a great variety ofshades can be achieved under mild conditions gentle to the hair.

Hence, the object of the present invention is an agent for dyeing fibers(A), for example wool, silk, cotton or hair and particularly human hair,which is prepared by mixing two components (A1) and (A2) and ischaracterized in that component (A1) contains at least one compound offormula (I)

wherein X denotes a halogen atom (F, Cl, Br, I), a methoxy group or anethoxy group; Y denotes an oxygen atom, a sulfur atom or a seleniumatom; R1 and R2 are equal or different and independently of each otherdenote hydrogen, a halogen atom (F, Cl, Br, I), a (C₁-C₄)-alkyl group, a(C₁-C₄)-alkyl group substituted with a halogen atom (F, Cl, Br, I), a(C₁-C₄)-alkoxy group, a nitro group, an acetamido group or anNR^(a)R^(b) group, wherein the R^(a) and R^(b) groups are equal ordifferent and independently of each other denote hydrogen, a(C₁-C₄)-alkyl group, an optionally substituted aromatic carbon ring or a(C₁-C₄)-alkanecarbonyl group, or R^(a) and R^(b) together with thenitrogen atom form a heterocyclic (C₃-C₆) group (for example animidazolidino, piperidino, pyrrolidino, pyrazolidino, piperazino ormorpholino group); and component (A2) contains at least one compoundselected from the group consisting of amines, aminonitrobenzenes andphenols.

Suitable compounds of formula (I) are, in particular, the following4-nitro-2,1,3-benzoxadiazoles, 4-nitro-2,1,3-benzothiadiazoles and4-nitro-2,1,3-benzoselenadiazoles:

4-chloro-7-nitro-2,1,3-benzoxadiazole;4-bromo-7-nitro-2,1,3-benzoxadiazole;4-fluoro-7-nitro-2,1,3-benzoxadiazole;4-methoxy-7-nitro-2,1,3-benzoxediazole;4-ethoxy-7-nitro-2,1,3-benzoxadiazole;4-chloro-5,7-dinitro-2,1,3-benzoxadiazole;5,7-dichloro-4-nitro-2,1,3-benzoxadiazole;5,7-dibromo-4-nitro-2,1,3-benzoxadiazole;7-chloro-4-nitro-5-diethylamino-2,1,3-benzoxadiazole;5-amino-7-chloro-4-nitro-2,1,3-benzoxadiazole;7-chloro-4-nitro-5-(1-piperidinyl)-2,1,3-benzoxadiazole;4-chloro-7-nitro-2,1,3-benzothiadiazole;4-bromo-7-nitro-2,1,3-benzothiadiazole;4-methoxy-7-nitro-2,1,3-benzothiadiazole;4-ethoxy-7-nitro-2,1,3-benzothiadiazole;4-chloro-5,7-dinitro-2,1,3-benzothiadiazole;4-bromo-5,7-dinitro-2,1,3-benzothiadiazole,4,5-dichloro-7-nitro-2,1,3-benzothiadiazole;5,7-dichloro-4-nitro-2,1,3-benzothiadiazole;4,5-dibromo-7-nitro-2,1,3-benzothiadiazole;5,7-dibromo-4-nitro-2,1,3-benzothiadiazole;4,6-dichloro-5,7-dinitro-2,1,3-benzothiadiazole;4,6-dibromo-5,7-dinitro-2,1,3-benzothiadiazole;5-chloro-7-fluoro-4-nitro-2,1,3-benzothiadiazole;5-anilino-7-bromo-4-nitro-2,1,3-benzothiadiazole;5-amino-7-chloro-4-nitro-2,1,3-benzothiadiazole;7-bromo-5-(diethylamino)-4-nitro-2,1,3-benzothiadiazole;4-chloro-5-methyl-7-nitro-2,1,3-benzothiadiazole;4-bromo-5-methyl-4-nitro-2,1,3-benzothiadiazole;7-bromo-5-(bromomethyl)-7-nitro-2,1,3-benzothiadiazole;N-(7-chloro-4-nitro-2,1,3-benzothiadiazole-5-yl)acetamide;4-chloro-7-nitro-2,1,3-benzoselenadiazole;4-bromo-7-nitro-2,1,3-benzoselenadiazole;4-methoxy-7-nitro-2,1,3-benzoselenadiazole;4-ethoxy-7-nitro-2,1,3-benzoselenadiazole;5,7-dibromo-4-nitro-2,1,3-benzoselenadiazole;5,7-dichloro-4-nitro-2,1,3-benzoselenadiazole;7-bromo-5-methyl-4-nitro-2,1,3-benzoselenadiazole and7-bromo-5-(bromomethyl)-4-nitro-2,1,3-benzoselenadiazole, among whichthe following compounds are particularly preferred:4-chloro-7-nitro-2,1,3-benzoxadiazole;4-bromo-7-nitro-2,1,3-benzoxadiazole;4-chloro-7-nitro-2,1,3-benzothiadiazole;4-bromo-7-nitro-2,1,3-benzothiadiazole;4-chloro-7-nitro-2,1,3-benzoselenadiazole and4-bromo-7-nitro-2,1,3-benzoselenadiazole.

Some of the compounds of formula (I) are commercially available. Thecompounds of formula (I), however, can also be prepared by methods ofsynthesis known from the literature, for example as described in theJournal of Organic Chemistry 36 (1), pages 207-209 (1971); Recueil Trav.Chim. Pays-Bas 86 (12), pages 1159-1181 (1967); Journal of MedicinalChemistry, vol 17 (2), pages 203-206 (1974); Journal of the ChemicalSociety (B), 1967, pages 909-911 or in U.S. Pat. No. 3,577,427.

Suitable amines are aliphatic or aromatic (isocyclic or heterocyclic)compounds with at least one amino group. Suitable aminonitrobenzenes arearomatic (isocyclic or heterocyclic) compounds with at least one nitrogroup and at least one amino group, and suitable phenols are aromatic(isocyclic or heterocyclic) compounds with at least one hydroxyl group.Examples of the amines, aminonitrobenzenes and phenols contained incomponent (A2) are, in particular, the following:

ethanolamine; propylamine; 3-amino-1-propanol; butylamine;4-amino-1-butanol; 1,4-diaminobenzene (p-phenylenediamine);1,4-diamino-2-methylbenzene (p-toluylenediamine);1,4-diamino-2,6-dimethylbenzene; 1,4-diamino-3,5-diethylbenzene;1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene;2-chloro-1,4-diaminobenzene; 2,5-diaminobiphenyl;1,4-diamino-2-hydroxymethylbenzene;1,4-diamino-2-(2-hydroxyethoxy)benzene;2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene; N-methylaniline;4-phenylaminoaniline; 4-dimethylaminoaniline; 4-diethylaminoaniline;4-dipropylaminoaniline; 4-[ethyl(2-hydroxyethyl)amino]aniline;4-[di(2′-hydroxyethyl)amino]aniline;4-[di(2-hydroxyethyl)amino]-2-methylaniline;4-[(2′-methoxyethyl)amino]aniline; 4-[(3′-hydroxypropyl)amino]aniline;4-[(2,3-dihydroxypropyl)amino]aniline;1,4-diamino-2-(2′-hydroxyethyl)benzene;1,4-diamino-2-(1′-hydroxyethyl)benzene;1,4-diamino-2-(1′-methylethyl)benzene;1,4-diamino-2-(methoxymethyl)benzene;1,4-diamino-2-(aminomethyl)benzene; 1,3-bis-[(4′-aminophenyl)(2′-hydroxyethyl)amino]-2-propanol;1,4-bis-[(4-aminophenyl)amino]butane;1,8-bis-(2′,5′-diaminophenoxy)-3,6-dioxaoctane; phenol; hydroquinone;2-methylphenol; 3-methylphenol; 4-methylphenol;5-methyl-2-(1′-methylethyl)phenol; 4-aminophenol;4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol;4-amino-3-fluorophenol; 4-methylaminophenol;4-amino-2-(aminomethyl)phenol; 4-amino-2-(hydroxymethyl)phenol;4-amino-2-fluorophenol; 4-amino-[(2′-hydroxyethyl)amino]-methylphenol;4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol;4-amino-2-(2′-hydroxyethyl)phenol; 5-aminosalicylic acid;2,5-diaminopyridine; 2,4,5,6-tetraaminopyrimidine;2,5,6-triamino-4-(1H)-pyrimidone;4,5-diamino-1-(4′-methyl-benzyl)-1H-pyrazole; 4,5-diamino-1H-pyrazole;4,5-diamino-1-(4′-methoxybenzyl)-1H-pyrazole;4,5-diamino-1-(3′-methoxybenzyl)-1H-pyrazole;4,5-diamino-1-(4′-chlorobenzyl)-1H-pyrazole;4,5-diamino-1-(4′-methylphenyl)-1H-pyrazole;4,5-diamino-1-(4′-methoxyphenyl)-1H-pyrazole;4,5-diamino-1-(3′-methoxyphenyl)-1H-pyrazole;4,5-diamino-1-(4′-chlorophenyl)-1H-pyrazole;4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 4,5-diamino-1-ethyl-1H-pyrazole;4-amino-1-[(4′-methoxyphenyl)methyl]-5-(methylamino)-1H-pyrazole;4-amino-5-[(2′-hydroxyethyl)amino]-1-(phenylmethyl)-1H-pyrazole;4,5-diamino-1-methyl-3-phenyl-1H-pyrazole;4,5-diamino-1-(2′-hydroxyethyl)-3-phenyl-1H-pyrazole;4,5-diamino-1,3-dimethyl-1H-pyrazole;4,5-diamino-3-methyl-1-phenyl-1H-pyrazole;4,5-diamino-1-(1-isopropyl)-1H-pyrazole; 2-aminophenol;2-amino-6-methylphenol; 2-amino-5-methylphenol;1,4-diamino-2-(thiophen-2-yl)benzene;1,4-diamino-2-(thiophen-3-yl)benzene;1,4-diamino-2-(pyridin-3-yl)benzene; 1,2,4-trihydroxybenzene;N-(3-dimethylaminophenyl)urea; 2,6-diaminopyridine;2-amino-4-[(2′-hydroxyethyl)-amino]anisole;2,4-diamino-1-fluoro-5-methylbenzene;2,4-diamino-1-methoxy-5-methylbenzene;2,4-diamino-1-ethoxy-5-methylbenzene;2,4-diamino-1-(2′-hydroxyethoxy)-5-methylbenzene;2,4-di-[(2′-hydroxyethyl)amino]-1,5-dimethoxybenzene;2,3-diamino-6-methoxypyridine;3-amino-6-methoxy-2-(methylamino)pyridine;2,6-diamino-3,5-dimethoxypyridine; 3,5-diamino-2,6-dimethoxypyridine;1,3-diaminobenzene (m-phenylenediamine);2,4-diamino-1-(2′-hydroxyethoxy)benzene; 2,4-diamino-1,5-di(2′-hydroxyethoxy)benzene; 1,3-diamino-4-(2,3-dihydroxypropoxy)benzene;1,3-diamino-4-(3-hydroxypropoxy)benzene;1,3-diamino-4-(2-methoxyethoxy)benzene;1-(2′-aminoethoxy)-2,4-diaminobenzene;2-amino-1-(2′-hydroxyethoxy)-4-methylaminobenzene;2,4-diaminophenoxyacetic acid; 3-[di(2′-hydroxyethyl)amino]aniline;4-amino-2-di[(2′-hydroxyethyl)amino]-1-ethoxybenzene;5-methyl-2-(1-methylethyl)phenol; 3-[(2′-hydroxyethyl)amino]aniline;3-[(2′-aminoethyl)amino]aniline; 1,3-2′,4′-diaminophenoxy)propane;di(2′,4′-diaminophenoxy)methane; 1,3-diamino-2,4-dimethoxybenzene;2,6-bis-(2′-hydroxyethyl)aminotoluene; 4-hydroxyindole;3-dimethylaminophenol; 3-diethylaminophenol; 5-amino-2-methylphenol;5-amino-4-fluoro-2-methylphenol; 5-amino-4-methoxy-2-methylphenol;5-amino-4-ethoxy-2-methylphenol; 3-amino-2,4-dichlorophenol;5-amino-2,4-dichlorophenol; 3-amino-2-methylphenol;3-amino-2-chloro-6-methylphenol; 3-aminophenol;N-[(3′-hydroxyphenyl)amino]acetamide;5-[(2-hydroxyethyl)amino-2-methylphenol;5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol;3-[(2′-hydroxyethyl)amino]phenol; 3-[(2′-methoxyethyl)-amino]phenol;5-amino-2-ethylphenol; 5-amino-2-methoxyphenol;2-(4′-amino-2′-hydroxyphenoxy)ethanol;5-[(3′-hydroxypropyl)amino]-2-methylphenol;3-[(2′,3′-dihydroxy)propylamino]-2-methylphenol;3-[(2′-hydroxyethyl)amino]-2-methylphenol; 2-amino-3-hydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 5-amino-4-chloro-2-methylphenol;1-naphthol; 1,5-dihydroxynaphthalene; 1,7-dihydroxynaphthalene;2,3-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; 2-methyl-1-naphtholacetate; 1,3-dihydroxybenzene (resorcinol);1-chloro-2,4-dihydroxybenzene; 2-chloro-1,3-dihydroxybenzene;1,2-dichloro-3,5-dihydroxy-4-methylbenzene;1,5-dichloro-2,4-dihydroxybenzene; 1,3-dihydroxy-2-methylbenzene;3,4-methylenedioxyphenol; 3,4-methylenedioxyaniline;5-[(2′-hydroxyethyl)amino]-1,3-benzodioxole;6-bromo-1-hydroxy-3,4-methylenedioxybenzene; 3,4-diaminobenzoic acid;3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine;6-amino-3,4-dihydro-1,4(2H)-benzoxazine; 3-methyl-1-phenyl-5-pyrazolone;5,6-dihydroxyindole; 5,6-dihydroxyindoline; 5-hydroxyindole;6-hydroxyindole; 7-hydroxyindole and 2,3-indolindione;1,4-bis-[2′-hydroxyethyl)amino]-2-nitrobenzene;1-(2′-hydroxyethyl)-amino-2-nitro-4-[di(2′-hydroxyethyl)amino]benzene;1-amino-3-methyl-4-[(2′-hydroxyethyl)amino]-6-nitrobenzene;4-[ethyl-(2′-hydroxyethyl)amino]-1-[(2′-hydroxyethyl)amino]-2-nitrobenzenehydrochloride;4-[di(2′-hydroxyethyl)amino]-1-[(2′-methoxyethyl)amino]-2-nitrobenzene;1-[(2′,3′-dihydroxypropyl)amino]-4-methyl-(2′-hydroxyethyl)amino]-2-nitrobenzene;1-[(2′,3′-dihydroxypropyl)amino]-4-ethyl-(2′-hydroxyethyl)amino]-2-nitrobenzenehydrochloride;1-(3′-hydroxypropylamino)-4-[(di-(2′-hydroxyethyl)amino]-2-nitrobenzene;1-methylamino-4-[methyl-(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene;2-[(4-amino-2-nitrophenyl)-amino]-5-dimethylaminobenzoic acid;1-(2′-aminoethylamino)-4-[(di(2′-hydroxyethyl)-amino]-2-nitrobenzene;1-amino-4-[(2′-hydroxyethyl)amino]-2-nitrobenzene;2-amino-4,6-dinitrophenol; 1,4-diamino-2-nitrobenzene;4-amino-2-nitrodiphenylamine;1-amino-4-[(di(2′-hydroxyethyl)amino]-2-nitrobenzene hydrochloride;1-amino-5-chloro-4-[(2′-hydroxyethyl)amino]-2-nitrobenzene;4-amino-1-[(2′-hydroxyethyl)amino]-2-nitrobenzene;4-[(2′-hydroxyethyl)methylamino]-1-(methylamino)-2-nitrobenzene;1-amino-4-[(2′,3′-dihydroxypropyl)amino]-5-methyl-2-nitrobenzene;1-amino-4-(methylamino)-2-nitrobenzene;4-amino-2-nitro-1-[(prop-2-en-1-yl)amino]benzene; 4-amino-3-nitrophenol;4-[(2′-hydroxyethyl)amino]-3-nitrophenol;4-[(2-nitrophenyl)amino]phenol;1-[(2′-aminoethyl)amino]-4-(2′-hydroxyethoxy)-2-nitrobenzene;4-(2′,3′-di-hydroxypropoxy)-1-[(2′-hydroxyethyl)amino]-2-nitrobenzene;1-amino-5-chloro-4-[(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene;5-chloro-1,4-[di-(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene;2-[(2′-hydroxyethyl)amino]-4,6-dinitrophenol;4-ethylamino-3-nitrobenzoic acid;2-[(4′-amino-2′-nitrophenyl)amino]benzoic acid;2-chloro-6-ethylamino-4-nitrophenol; 2-amino-6-chloro-4-nitrophenol;4-[(3′-hydroxypropyl)-amino]-3-nitrophenol; 2,5-diamino-6-nitropyridine;6-amino-3-[(2′-hydroxyethyl)amino]-2-nitropyridine;3-amino-6-[(2′-hydroxyethyl)amino]-2-nitropyridine;3-amino-6-(ethylamino)-2-nitropyridine;3-[(2′-hydroxyethyl)amino]-6-(methylamino)-2-nitropyridine;3-amino-6-(methylamino)-2-nitropyridine;6-(ethylamino)-3-[(2′-hydroxyethyl)amino]-2-nitropyridine;1,2,3,4-tetrahydro-6-nitro-quinoxaline;7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine;1,2-diamino-4-nitrobenzene;1-amino-2-[(2′-hydroxyethyl)-amino]-5-nitrobenzene;1-(2′-hydroxyethoxy)-2-[(2′-hydroxyethyl)amino]-5-nitrobenzene;1-[(2′-hydroxyethyl)amino]-2-nitrobenzene;2-(di(2′-hydroxyethyl)amino]-5-nitrophenol;2-[(2′-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene;2-amino-3-nitrophenol; 1-amino-2-methyl-6-nitrobenzene;1-(2′-hydroxyethoxy)-3-methylamino-4-nitrobenzene;2,3-(dihydroxypropoxy)-3-methylamino-4-nitrobenzene;2-[(2′-hydroxyethyl)amino]-5-nitrophenol;3-[(2′-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride;1-[(2′-ureidoethyl)amino]-4-nitrobenzene;4-[(2′,3′-dihydroxypropyl)-amino]-3-nitro-1-trifluoromethylbenzene;1-chloro-2,4-bis-[(2′-hydroxyethyl)amino]-5-nitrobenzene;1-amino-4-[(2′-aminoethyl)amino]-5-methyl-2-nitrobenzene;4-[(2′-hydroxyethyl)amino]-3-nitro-1-methylbenzene;1-chloro-4-[(2′-hydroxyethyl)amino]-3-nitrobenzene;4-[(2′-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene;4-[(2′-hydroxyethyl)amino]-3-nitrobenzonitrile;4-[(2′-hydroxyethyl)amino]-3-nitrobenzamide;3-[(2′-hydroxyethyl)amino]-4-methyl-1-nitrobenzene and4-chloro-3-[(2′-hydroxyethyl)amino]-1-nitrobenzene.

Particularly preferred amines, aminonitrobenzenes or phenols areethanolamine, 1,4-diaminobenzene; 1,4-diamino-2-methylbenzene;1,4-diamino-2-(2′-hydroxyethyl)-benzene;1,4-diamino-2-(1′-hydroxyethyl)benzene;2,4-diamino-1-(2′-hydroxyethoxy)benzene; 2,4,5,6-tetraaminopyrimidine;hydroquinone; 5,6-diamino-2,4-dihydroxy-pyrimidine; 2,7-diaminofluorene;1-amino-2-naphthol; 2,3-dihydro-3-methyl-2-benzothiazolone hydrazone;2-aminophenol; 4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-benzyl-1H-pyrazole; phenol;4,5-diamino-1-[(4′-methylbenzyl)-1H-pyrazole; 4,5-diamino-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 4,5-diamino-(1-isopropyl)-1H-pyrazole;N-(3-dimethylaminophenyl)urea;2-amino-4-[(2′-hydroxyethyl)amino]anisole; 1,3-diaminobenzene;1,3-di[(2,4-diaminophenoxy)propane; 4-methylphenol; 4-aminophenol;4-amino-3-methylphenol; 5-amino-2-methylphenol; 3-aminophenol;1,3-dihydroxybenzene; 5-hydroxyindole;4-[(2′-hydroxyethyl)amino]-3-nitro-1-methylbenzene;4-[(2′-hydroxyethyl)amino]-3-nitrophenol;2-amino-6-chloro-4-nitrophenol; 2-chloro-6-ethylamino-4-nitrophenol;1-amino-2-[(2′-hydroxyethyl)-amino]-5-nitrobenzene as well as the2,5-diaminonitrobenzenes, for example1-(2′-hydroxyethyl)amino-2-nitro-4-[(di(2′-hydroxyethyl)amino]benzene,1-amino-4-[di(2′-hydroxyethyl)amino]-2-nitrobenzene;4-[di(2′-hydroxyethyl)amino]-1-[(2′-methoxyethyl)amino]-2-nitrobenzene;4-[ethyl-(2′-hydroxyethyl)amino]-1-[(2′-hydroxy-ethyl)amino]-2-nitrobenzene;1-amino-5-chloro-4-[(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene and2,5-diamino-6-nitropyridine.

The compounds of formula (I) and the amines, aminonitrobenzenes orphenols are kept separate from each other and are mixed with each othershortly before use. If the compounds of formula (I) and the amines,aminonitrobenzenes and/or phenols are solids, however, it is alsopossible to package them together and to prepare the ready-for-usecolorant (A) shortly before use by mixing the compounds of formula (I)and the amines, aminonitrobenzenes and/or phenols with water or with aliquid preparation containing the remaining constituents of the coloringagent.

Moreover, In addition to the compounds of formula (I) and to the amines,aminonitrobenzenes and phenols, the colorant of the invention canoptionally contain in component (A2) and in the ready-for-usepreparation (A) other common, physiologically innocuous, direct dyesfrom the group consisting of cationic and anionic dyes, disperse dyes,azo dyes, quinone dyes and triphenylmethane dyes.

These direct dyes can be used in component (A2) in a total amount fromabout 0.02 to about 20 wt. % and preferably from 0.2 to 10 wt. %, thetotal amount of direct dyes in the ready-for-use colorant (A) obtainedby mixing components (A1) and (A2) being about 0.01 to about 10 wt. %and preferably 0.1 to 5 wt. %.

As a rule, the coloring agent of the invention consists of a mixture ofcomponents (A1) and (A2), namely of a dye carrier composition (A1) whichcontains the compound of formula (I), and an additional dye carriercomposition (A2) which contains the amines, aminonitrobenzenes and/orphenols.

The compounds of formula (I) and the amines, aminonitrobenzenes and/orphenols are contained in their respective dye carrier composition[component (A1) or component (A2)] in a total amount from about 0.02 toabout 20 wt. % and preferably from about 0.2 to about 10 wt. %, thecompounds of formula (I) and the amines, aminonitrobenzenes and/orphenols being contained in the ready-for-use coloring agent (A) in atotal amount from about 0.01 to about 10 wt. % and preferably from about0.1 to about 5 wt. %.

Components (A1) and (A2) and the ready-for-use coloring agent (A) can beprepared in the form of a solution, particularly an aqueous oraqueous-alcoholic solution, or as a cream, a gel or an emulsion. Such apreparation consists of a mixture of the compound of formula (I) and ofthe amines, aminonitrobenzenes and/or phenols with the additivescommonly used in such preparations.

Common additives for colorants used in the form of solutions, creams,emulsions, gels or aerosol foams are, for example, solvents such aswater, the lower aliphatic alcohols, for example ethanol, n-propanol andisopropanol, or the polyols such as glycerol and 1,2-propandiol,moreover wetting agents or emulsifiers from the classes of anionic,cationic, amphoteric or nonionic surface-active substances such as thefatty alcohol sulfates, ethoxylated fatty alcohol sulfates,alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts,alkylbetaines, ethoxylated fatty alcohols*¹, ethoxylated nonylphenols*,fatty alkanolamides*, ethoxylated fatty esters, moreover thickeners suchas the higher fatty alcohols, starch or cellulose derivatives, perfumes,hair-pretreatment agents, conditioners, hair swelling agents,preservatives, furthermore vaselines, paraffin oils and fatty acids aswell as hair-care agents such as cationic resins, lanolin derivatives,cholesterol, pantothenic acid and betaine. The said constituents areused in amounts commonly employed for such purposes, for example thewetting agents and emulsifiers at a concentration of about 0.5 to about30 wt. % [always based on component (A1) or (A2)], the thickeners in anamount from about 0.1 to about 25 wt. % [always based on component (A1)or component (A2)], and the hair-care agents at a concentration of about0.1 to about 5.0 wt. % [always based on component (A1) or component(A2)].

¹In the original German text, the compounds marked with an asteriskappear twice, obviously by mistake—Translator

The pH of the ready-for-use colorant (A) is about 3 to about 12 andpreferably about 4 to about 10 and as a rule is reached upon mixingcomponent (A1) with component (A2). To adjust the pH of components (A1)and (A2) and of the ready-for-use colorant (A) to the value desired forthe dyeing, an alkalinizing agent can be used if needed, for example analkali metal hydroxide, alkaline earth metal hydroxide, alkali metalacetate, alkaline earth metal acetate, alkali metal carbonate oralkaline earth metal carbonate, or an acid, for example lactic acid,acetic acid, tartaric acid, phosphoric acid, hydrochloric acid, citricacid, ascorbic acid or boric acid.

The ready-for-use colorant is prepared just before use by mixingcomponents (A1) and (A2), optionally by adding a base, for examplesodium acetate, sodium bicarbonate or sodium carbonate, and is thenapplied to the fibers, particularly human hair. Depending on the depthof shade desired, this mixture is allowed to act for about 5 to about 60minutes and preferably from about 15 to about 30 minutes at atemperature of about 20 to about 50° C. and particularly from about 30to about 40° C. The fibers are then rinsed with water, optionally washedwith a shampoo and then dried.

Another object of the present invention is a multicomponent kitconsisting of a preparation of component (A1), a preparation ofcomponent (A2) and optionally an agent for adjusting the pH. Thepreparations of components (A1) and (A2) can, of course, also consistsof several individual components which are mixed just before use. A2-component kit is also possible, in which case the first componentconsists of a powder of a compound of formula (I), the amine,aminonitrobenzene and/or phenol and optionally other common powderedcosmetic additives, and the second component is water or a liquidcosmetic preparation. Particularly preferred, however, is a 2-componentkit consisting of a preparation of component (A1) and a preparation ofcomponent (A2).

The coloring agent of the invention imparts to the fibers, particularlykeratin fibers such as human hair, in a gentle manner, a uniform andlong-lasting coloration, a wide range of yellow to dark-violet orbrown-black color shades being possible.

Because of their high resistance to oxidants, the compounds of generalformula (I) can also be used in oxidative colorants based on oxidationdye precursors. It is also possible to use the compounds of generalformula (I) in brightening toners in which—for the purpose ofbrightening the hair to be dyed or of improving its luster—the directdyes are used in combination with an oxidant.

The following examples illustrate the object of the invention withoutlimiting its scope.

EXAMPLES Examples 1 to 21 Hair Colorants

Component (A1) 0.5 g of 7-chloro-4-nitro-2,1,3-benzoxadiazole 5.0 g ofethanol 4.0 g of decyl polyglucoside (aqueous solution; Plantaren ®2000, supplied by Cognis, Germany) 0.2 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralizedComponent (A2) X g of powdered amine and/or phenol as per Table 1.

The aforesaid mixture [component (A1)] was mixed uniformly with thepowder containing the amine or the phenol [component (A2)] at roomtemperature (20-25° C.) or with slight heating (35-40° C.)—optionally byadding a spatula tip-full of sodium acetate. If necessary, the pH wasadjusted to the desired value with sodium hydroxide or citric acid.

The ready-for-use hair colorant thus obtained was applied to the hairand uniformly distributed with a brush. After an exposure time of 30 minat 40° C., the hair was rinsed with lukewarm water and then dried.

The amount of amine or phenol used and the resulting colorations aresummarized in the following Table 1.

TABLE 1 Ex- ample Amine or Phenol Shade After Color values No. Used(amount in g) pH Dyeing L a b 1 ethanolamine 9.3 yellow +41.16 +11.42+43.41 (0.153 g) 2 phenol (0.235 g) 3.5 yellow +57.82 +8.43 +62.90 3hydroquinone 7.0 orange +69.52 +2.72 +46.43 (0.275 g) 4 4-dimethylamino-4.6 violet +31.83 +13.15 −2.80 aniline (0.340 g) 5 1,4-diaminobenzene4.7 violet +26.36 +23.37 −0.48 (0.270 g) 6 1,4-diamino-2- 4.5 violet+30.81 +21.60 +0.28 methylbenzene.HCl (0.055 g) 7 1,4-diamino-2-(2- 3.9violet +21.33 +17.74 +2.16 hydroxyethyl)- benzene sulfate (0.630 g) 84-aminophenol 3.4 ruby-red +26.13 +39.62 +15.48 (0.273 g) 92,4,5,6-tetraamino- 9.8 green-brown +34.85 +4.30 +18.31 pyrimidinesulfate (0.640 g) 10 5,6-diamino-2,4-di- 7.3 brown-orange +32.73 +15.18+28.79 hydroxypyrimidine sulfate (0.455 g) 11 4,5-diamino-1-(2′- 9.3 red+29.07 +38.14 +22.13 hydroxyethyl)-1H- pyrazole sulfate (0.600 g) 122,7-diaminofluorene 7.4 violet +26.95 +18.76 +5.13 (0.490 g) 131-amino-2-naphthol. 6.3 brown +41.52 +7.03 +20.43 HCl (0.489 g) 142,3-dihydro-3-methyl- 6.4 orange +44.00 +40.62 +46.52 2-benzothiazolonehydrazone.HCl (0.584 g) 15 N-(3-dimethylamino- 6.5 yellow-brown +35.42+1.75 +14.81 phenyl)urea (0.448 g) 16 2-amino-4-[(2′-hy- 6.7 gray +47.79−2.78 +1.60 droxyethyl)amino]- anisole sulfate (0.746 g) 171,3-diaminobenzene 4.3 red-violet +32.31 +18.33 +11.25 (0.270 g) 182,4-diamino-1-(2′- 4.1 blue-violet +26.41 +4.77 −2.69 hydroxyethoxy)ben-zene sulfate (0.666 g) 19 5-amino-2-methyl- 4.5 ruby-red +32.96 +39.20+24.27 phenol (0.308 g) 20 3-aminophenol 4.4 ruby-red +38.98 +40.37+34.32 (0.273 g) 21 1,3-dihydroxy- 4.0 yellow +70.64 +8.37 +47.07benzene (0.275 g)

Examples 22 to 28 Hair Colorants

Component (A1): 1.0 g of 7-chloro-4-nitro-2,1,3-benzoxadiazole 5.0 g ofethanol 4.0 g of decyl polyglucoside (Plantaren ® 2000), aqueoussolution 0.2 g of disodium ethylenediaminetetraacetate hydrate to 100.0g water, demineralized Component (A2): X g of amine or phenol as perTable 2 5.0 g of ethanol 4.0 g of decyl polyglucoside (Plantaren ®2000), aqueous solution 0.2 g of disodium ethylenediaminetetraacetatehydrate to 100.0 g water, demineralized

10 g of component (A1) was mixed uniformly with 10 g of component (A2)at room temperature (20-25° C.) or with slight heating (35-40°C.)—optionally by adding a spatula tip-full of sodium acetate. Ifnecessary, the pH was adjusted to the desired value with sodiumhydroxide or citric acid.

The ready-for-use hair colorant thus obtained was applied to the hairand uniformly distributed with a brush. After an exposure time of 30 minat 40° C., the hair was rinsed with lukewarm water and then dried.

The amount of amine or phenol used and the resulting colorations aresummarized in the following Table 2.

TABLE 2 Ex- ample Amine or Phenol Shade After Color values No. Used(amount in g) pH Dyeing L a b 22 1,4-diaminobenzene 4.8 violet +21.77+20.65 +0.80 (0.540 g) 6.8 +26.66 +25.47 −1.39 9.8 +30.48 +24.70 −0.3523 1,4-diamino-2- 4.7 violet +21.69 +19.99 +3.57 methylbenzene 6.8+29.24 +22.23 +5.84 sulfate (1.100 g) 10.0 +30.14 +19.04 +4.62 244-aminophenol 4.6 ruby-red +23.87 +35.97 +13.01 (0.546 g) 6.9 +25.30+39.15 +14.64 9.5 +23.31 +35.70 +12.80 25 2-aminophenol 4.8 red-orange+34.39 +40.22 +29.97 (0.546 g) 6.6 +34.59 +39.94 + 30.89 9.2 +32.15+34.18 +38.30 26 phenol 4.7 yellow +67.34 +6.41 +76.05 (0.470 g) 6.8 +62.29 + 9.85 + 73.75 9.8 +68.61 +4.33 +70.47 27 phenol (0.234 g) 4.3pink-violet +43.82 +22.25 +12.60 and 1,4-diamino-2- 7.7 +47.73 +20.71+8.74 methylbenzene sul- 10.0 +37.17 +20.80 +2.67 fate (0.550 g) 282-aminophenol 4.4 ruby-red +23.96 +35.28 +13.08 (0.272 g) and 7.7 +21.82+30.59 + 10.46 4-aminophenol 9.5 +21.95 +27.56 +10.03 (0.272 g)

Examples 29 and 30 Hair Colorants in Cream Form

Component (A1):  1 g of 7-chloro-4-nitro-2,1,3-benzoxadiazole 12 g ofcetearyl alcohol 10 g of lauryl ether sulfate, 28% aqueous solution 20 gof ethanol to 100 g water, demineralized

The cetearyl alcohol was melted at 80° C. The lauryl ether sulfate washeated to 80° C. with 95% of the water and added to the molten cetearylalcohol. The mixture was stirred until a cream formed. The7-chloro-4-nitro-2,1,3-benzoxadiazole was mixed with the ethanol and theremainder of the water at room temperature and the resulting mixture wasadded to the cream. The pH of the cream thus obtained was 4.6.

Component (A2) X g of the amine or phenol as per Table 3 12 g ofcetearyl alcohol 10 g of lauryl ether sulfate, 28% aqueous solution 20 gof ethanol to 100 g water, demineralized

The cetearyl alcohol was melted at 80° C. The lauryl ether sulfate washeated to 80° C. with 95% of the water and added to the molten cetearylalcohol. The mixture was stirred until a cream formed. The amine or thephenol was mixed with the ethanol and the remainder of the water at roomtemperature, and the resulting mixture was added to the cream. The pH ofthe cream thus obtained was adjusted to 7 (optionally with addition ofsodium acetate).

Components (A1) and (A2) were mixed with one another in a 1:1 ratio.Optionally a spatula tip-full of sodium acetate was added. If needed,the pH of the ready-for-use colorant was adjusted to the desired valuewith sodium hydroxide or citric acid. The resulting ready-for-use haircolorant was applied to the hair and uniformly distributed with a brush.After an exposure time of 30 min at 40° C., the hair was washed with ashampoo, rinsed with lukewarm water and then dried.

The amount of amine or phenol used and the resulting colorations aresummarized in the following Table 3.

TABLE 3 Ex- ample Amine or Phenol Shade After Color values No. Used(amount in g) pH Dyeing L a b 29 1,4-diaminobenzene 7.2 violet +20.8+20.3 +1.4 (1.350 g) 30 4-aminophenol 7.3 ruby-red +22.4 +35.7 +11.4(1.370 g)

Examples 31 to 42 Hair Colorants

Component (A1) 1.0 g of 7-chloro-4-nitro-2,1,3-benzoxadiazole 5.0 g ofethanol 4.0 g of decyl polyglucoside (aqueous solution; Plantaren ®2000, supplied by Cognis, Germany) 0.2 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralizedComponent (A2) X g of aminonitrobenzene as per Table 4 5.0 g of ethanol4.0 g of decyl polyglucoside (Plantaren ® 2000), aqueous solution 0.2 gof disodium ethylenediaminetetraacetate hydrate to 100.0 g water,demineralized

10 g of component (A1) was mixed uniformly with 10 g of component (A2)at room temperature (20-25° C.) or with slight heating (35-40°C.)—optionally by adding a spatula tip-full of sodium acetate. Ifnecessary, the mixture was heated at 40 to 60° C. for 15 minutes. Whenneeded, the pH was adjusted to the desired value with sodium hydroxideor citric acid.

The ready-for-use hair colorant thus obtained was applied to the hairand uniformly distributed with a brush. After an exposure time of 30 minat 40° C., the hair was rinsed with lukewarm water and then dried.

The amount of aminonitrobenzene used and the resulting colorations aresummarized in the following Table 4.

TABLE 4 Ex- ample Aminonitrobenzene Shade After Color values No. Used(amount in g) pH Dyeing L a b 31 1-(2′-hydroxyethyl)- 6.3 brown-black+17.19 +3.94 +2.43 amino-2-nitro-4-[(di- with violet (2′-hydroxyethyl)-reflexes amino]benzene (1.420 g) 32 4-di[(2′-hydroxy- 4.9 brown-black+18.47 +5.56 +3.59 ethyl)amino]-1- with violet [(2-methoxyethyl)-reflexes amino]-2-nitro- benzene (1.490 g) 33 4-[ethyl-(2′-hydroxy- 5.4brown-black +18.27 +3.45 +2.71 ethyl)amino]-1-[(2′- with violethydroxyethyl)amino]- reflexes 2-nitrobenzene.HCl (1.520 g) 341-amino-4-[di(2′- 5.2 brown with +18.10 +10.07 +3.93hydroxyethyl)amino]- red reflexes 2-nitrobenzene.HCl (1.200 g) 351-amino-5-chloro-4- 7.0 cherry-red +20.35 +24.84 +7.43[(2′,3′-dihydroxy- propyl)amino]-2- nitrobenzene (1.300 g) 361-amino-2-[(2′- 10.0 red-orange +29.98 +34.15 +23.20hydroxyethyl)amino]- 5-nitrobenzene (0.980 g) 37 4-[(2′-hydroxyethyl)-0.4 orange +51.18 +30.12 +59.68 amino]-3-nitro-1- methylbenzene (0.980g) 38 4-[(2′-hydroxyethyl)- 6.2 ruby-red +30.91 +48.81 +25.69amino]-3-nitro- phenol (0.990 g) 39 2-amino-6-chloro-4- 4.7 brown-violet+17.74 +15.06 +4.19 nitrophenol.HCl (1.120 g) 40 2-chloro-6-ethyl- 7.5red +29.73 +38.89 +23.40 amino-4-nitro- phenol (1.080 g) 412,5-diamino-6-nitro- 6.5 orange +39.10 +37.92 +40.11 pyridine (0.770 g)42 1-amino-4-[di(2′-hy- 4.8 brown with +18.76 +9.46 +3.08droxyethyl)amino]- red reflexes 2-nitrobenzene.HCl (0.60 g) and 4-[di-(2′-hydroxyethyl)- amino]-1-[(2′- methoxyethyl)- amino]-2-nitro- benzene(0.750 g)

Examples 43 to 51 Hair Colorants

Component (A1) 0.488 g  of 7-methoxy-4-nitro-2,1,3-benzoxadiazole  5.0 gof ethanol  4.0 g of decyl polyglucoside (aqueous solution; Plantaren ®2000, supplied by Cognis, Germany)  0.2 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralizedComponent (A2) X g of powdered amine and/or phenol as per Table 5.

The aforesaid mixture [component (A1)] was mixed uniformly with thepowder containing the amine or the phenol [component (A2)] at roomtemperature (20-25° C.) or with slight heating (35-40° C.)—optionally byadding a spatula tip-full of sodium acetate. If necessary, the pH wasadjusted to the desired value with sodium hydroxide or citric acid.

The ready-for-use hair colorant thus obtained was applied to the hairand uniformly distributed with a brush. After an exposure time of 30 minat 40° C., the hair was rinsed with lukewarm water and then dried.

The amount of amine or phenol used and the resulting colorations aresummarized in the following Table 5.

TABLE 5 Ex- ample Amine or Phenol Shade After Color values No. Used(amount in g) pH Dyeing L a b 43 1,4-diamino-2- 4.7 violet +21.82 +19.70+2.28 methylbenzene sulfate (0.55 g) 44 1,4-diamino-2-(2- 4.6 violet+17.75 +11.85 +1.25 hydroxyethyl)ben- zene sulfate (0.63 g) 454-aminophenol 7.6 ruby-red +31.05 +46.43 +20.06 (0.273 g) 464-amino-3-methyl- 9.3 orange +44.84 +32.42 +43.04 phenol [no amountgiven-Translator] 47 4,5-diamino-1- 9.9 red +28.26 +34.16 +17.99(2′-hydroxyethyl)- 1H-pyrazole sul- fate (0.600 g) 48 2,4-diamino-1-(2′-4.4 red-violet +28.41 +31.66 +11.88 hydroxyethoxy)- benzene sulfate(0.660 g) 49 5-amino-2-methyl- 4.7 red +46.23 +48.47 +28.73 phenol(0.308 g) 50 3-aminophenol 4.2 red-orange +44.08 +51.80 +44.28 (0.273 g)51 1,3-dihydroxy- 4.8 yellow +78.59 −0.89 +62.74 benzene (0.275 g)

The L*a*b* values given in the preceding examples were determined with aChromameter II color meter supplied by Minolta. The L value indicatesthe brightness (namely the lower the L value the higher is the colorintensity), whereas the a-value is a measure of the red content (namelythe higher the a-value the higher is the red content). The b-value is ameasure of the blue content of the color, the blue content being thehigher the more negative is the b-value.

Unless otherwise indicated, all percentages in the present patentapplication are by weight.

What is claimed is:
 1. Fiber-coloring agent (A) prepared by mixing twocomponents (A1) and (A2), characterized in that component (A1) containsat least one compound of formula (I)

wherein X denotes a halogen atom, a methoxy group or an ethoxy group; Ydenotes an oxygen atom, a sulfur atom or a selenium atom; R1 and R2 areequal or different and independently of each other denote hydrogen, ahalogen atom, a (C₁-C₄)-alkyl group, a halogen-substituted (C₁-C₄)-alkylgroup, a (C₁-C₄)-alkoxy group, a nitro group, an acetamido group or anNR^(a)R^(b) group, wherein the R^(a) and R^(b) groups are equal ordifferent and independently of each other denote hydrogen, a(C₁-C₄)-alkyl group, an optionally substituted aromatic carbon ring or a(C₁-C₄)-alkanecarbonyl group, or R^(a) and R^(b) together with thenitrogen atom form a heterocyclic (C₃-C₆) group; and component (A2)contains at least one compound selected from the group consisting ofamines, aminobenzenes and phenols.
 2. Agent according to claim 1,characterized in that the compound of formula (I) is selected from, thegroup consisting of 4-nitro-2,1,3-benzoxadiazoles,4-nitro-2,1,3-benzothiadiazoles 4-nitro-2,1,3-benzoselenadiazoles with4-chloro-7-nitro-2,1,3-benzoxadiazole;4-bromo-7-nitro-2,1,3-benzoxadiazole;4-fluoro-7-nitro-2,1,3-benzoxadiazole,4-methoxy-7-nitro-2,1,3-benzoxadiazole,4-ethoxy-7-nitro-2,1,3-benzoxadiazole,4-chloro-5,7-dinitro-2,1,3-benzoxadiazole,5,7-dichloro-4-nitro-2,1,3-benzoxadiazole,5,7-dibromo-4-nitro-2,1,3-benzoxadiazole,7-chloro-4-nitro-5-diethylamino-2,1,3-benzoxadiazole,5-amino-7-chloro-4-nitro-2,1,3-benzoxadiazole,7-chloro-4-nitro-5-(1-piperidinyl)-2,1,3-benzoxadiazole,4-chloro-7-nitro-2,1,3-benzothiadiazole,4-bromo-7-nitro-2,1,3-benzothiadiazole,4-methoxy-7-nitro-2,1,3-benzothiadiazole,4-ethoxy-7-nitro-2,1,3-benzothiadiazole,4-chloro-5,7-dinitro-2,1,3-benzothiadiazole,4-bromo-5,7-dinitro-2,1,3-benzothiadiazole,4,5-dichloro-7-nitro-2,1,3-benzothiadiazole,5,7-dichloro-4-nitro-2,1,3-benzothiadiazole,4,5-dibromo-7-nitro-2,1,3-benzothiadiazole,5,7-dibromo-4-nitro-2,1,3-benzothiadiazole,4,6-dichloro-5,7-dinitro-2,1,3-benzothiadiazole,4,6-dibromo-5,7-dinitro-2,1,3-benzothiadiazole,5-chloro-7-fluoro-4-nitro-2,1,3-benzothiadiazole,5-anilino-7-bromo-4-nitro-2,1,3-benzothiadiazole,5-amino-7-chloro-4-nitro-2,1,3-benzothiadiazole,7-bromo-5-(diethylamino)-4-nitro-2,1,3-benzothiadiazole,4-chloro-5-methyl-7-nitro-2,1,3-benzothiadiazole,4-bromo-5-methyl-4-nitro-2,1,3-benzothiadiazole,7-bromo-5-(bromomethyl)-7-nitro-2,1,3-benzothiadiazole,N-(7-chloro-4-nitro-2,1,3-benzothiadiazole-5-yl)acetamide,4-chloro-7-nitro-2,1,3-benzoselenadiazole;4-bromo-7-nitro-2,1,3-benzoselenadiazole,4-methoxy-7-nitro-2,1,3-benzoselenadiazole,4-ethoxy-7-nitro-2,1,3-benzoselenadiazole,5,7-dibromo-4-nitro-2,1,3-benzoselenadiazole,5,7-dichloro-4-nitro-2,1,3-benzoselenadiazole,7-bromo-5-methyl-4-nitro-2,1,3-benzoselenadiazole and7-bromo-5-(bromomethyl)-4-nitro-2,1,3-benzoselenadiazole.
 3. Agentaccording to claim 1, characterized in that the amine, aminonitrobenzeneand phenol are selected from the group consisting of ethanolamine,1,4-diaminobenzene, 1,4-diamino-2-methylbenzene,1,4-diamino-2-(2′-hydroxyethyl)benzene,1,4-diamino-2-(1′-hydroxyethyl)benzene,2,4-diamino-1-(2′-hydroxyethoxy)benzene, 2,4,5,6-tetraaminopyrimidine,hydroquinone, 5,6-diamino-2,4-dihydroxypyrimidine; 2,7-diaminofluorene;1-amino-2-naphthol, 2,3-dihydro-3-methyl-2-benzothiazolone hydrazone,2-aminophenol, 4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-benzyl-1H-pyrazole, phenol,4,5-diamino-1-[(4′-methylbenzyl)-1H-pyrazole, 4,5-diamino-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole, 4,5-diamino-(1-isopropyl)-1H-pyrazole,N-(3-dimethylaminophenyl)urea,2-amino-4-[(2′-hydroxyethyl)amino]anisole, 1,3-diaminobenzene,1,3-di(2,4-diaminophenoxy)propane, 4-methylphenol, 4-aminophenol,4-amino-3-methylphenol, 5-amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 5-hydroxyindole,4-[(2′-hydroxyethyl)amino]-3-nitro-1-methylbenzene,4-[(2′-hydroxyethyl)amino]-3-nitrophenol,2-amino-6-chloro-4-nitrophenol, 2-chloro-6-ethylamino-4-nitrophenol,1-amino-2-[(2′-hydroxyethyl)amino]-5-nitrobenzene as well as the2,5-diaminonitrobenzenes, for example1-(2′-hydroxyethyl)amino-2-nitro-4-[(di-(2′-hydroxyethyl)amino]benzene,1-amino-4-[di(2′-hydroxyethyl)amino]-2-nitrobenzene,4-[di(2′-hydroxyethyl)amino]-1-[(2′-methoxyethyl)amino]-2-nitrobenzene,4-[ethyl-(2′-hydroxyethyl)amino]-1-[(2′-hydroxyethyl)-amino]-2-nitrobenzene,1-amino-5-chloro-4-[(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene and2,5-diamino-6-nitropyridine.
 4. Agent according to claim 1,characterized in that the compounds of formula (I) and the amines,aminonitrobenzenes and/or phenols are contained in the dye carrier[component (A1) or component (A2)] in a total amount from 0.02 to 20 wt.%.
 5. Agent according to claim 1, characterized in that the compounds offormula (I) and the amines, aminonitrobenzenes and/or phenols arecontained in the ready-for-use hair colorant (A) in a total amount from0.01 to 10 wt. %.
 6. Agent according to claim 1, characterized in thatit contains additionally from 0.02 to 20 wt. % of a physiologicallyinnocuous, direct dye selected from the group consisting of cationic andanionic dyes, disperse dyes, nitro dyes, azo dyes, quinone dyes andtriphenylmethane dyes.
 7. Agent according to claim 1, characterized inthat the ready-for-use colorant (A) has a pH from 3 to
 12. 8. Agentaccording to claim 1, characterized in that it additionally contains anoxidation dye precursor.
 9. Agent according to claim 1, characterized inthat it is mixed with an oxidant before use.
 10. Agent according toclaim 1, characterized in that it is a hair-coloring agent. 11.Hair-dyeing method whereby the ready-for-use coloring agent (A) isprepared immediately before use by mixing two components (A1) and (A2),optionally with addition of sodium acetate, and is then applied to thehair and allowed to act for 5 to 60 minutes at a temperature of 20 to50° C., the hair then being rinsed with water, optionally washed with ashampoo, and then dried, characterized in that a coloring agent (A)obtained by mixing two components (A1) and (A2) according to claim 1 isused.
 12. Multicomponent kit for dyeing hair, consisting of apreparation of component (A1) according to claim 1 and of a preparationof (A2) according to one of claim 1 and optionally of an agent foradjusting the pH.
 13. Use of a combination of at least one compound offormula (I)

wherein X denotes a halogen atom, a methoxy group or an ethoxy group, Ydenotes an oxygen atom, a sulfur atom or a selenium atom, R1 and R2 areequal or different and independently of each other denote hydrogen, ahalogen atom, a (C₁-C₄)-alkyl group, a halogen-substituted (C₁-C₄)-alkylgroup, a (C₁-C₄)-alkoxy group, a nitro group, an acetamido group or anNR^(a)R^(b) group, wherein the R^(a) and R^(b) groups are equal ordifferent and independently of each other denote hydrogen, a(C₁-C₄)-alkyl group, an optionally substituted aromatic carbon ring or a(C₁-C₄)-alkanecarbonyl group, or R^(a) and R^(b) together with thenitrogen atom form a heterocyclic (C₃-C₆) group, and at least onecompound selected from the group consisting of amines,aminonitrobenzenes and phenols, for dyeing keratin fibers.